Light sensitive silver halide color photographic material

ABSTRACT

A compound of the formula:   WHEREIN N IS AN INTEGER OF 1 TO 4 AND R is a lower alkyl group is found to be useful as a cyan coupler providing auto-masking mechanism for light-sensitive color photographic materials so as to compensate for the deficient color reproductivity of said materials.

United States Patent [191 lwama et a1.

1 1 LIGHT SENSITIVE SILVER I-IALIDE COLOR PHOTOGRAPIIIC MATERIAL [75] Inventors: Masakuni lwama; Mitsuto Fujiwara;

Tamotsu Kojima; Toshihiko Yamamoto, all of Tokyo, Japan [73] Assignee: Konishiroku Photo Industry Co.,

Ltd., Tokyo, Japan [22] Filed: May 23, 1972 [21] Appl. No.2 256,010

Related U.S. Application Data [63] Continuation-impart of Ser. No. 28,083, April 13,

1970, abandoned.

[30] Foreign Application Priority Data Apr. 14, 1969 Japan 44-28287 [52] US. Cl. 96/100, 96/9 [51] Int. Cl G03c 1/40 [58] Field of Search...'......... 96/100, 9

[56] References Cited UNITED STATES PATENTS 3,034,892 5/1962 Gledhill et a1. 96/100 3,459,552 8/1969 Yoshida et a1 96/100 3,481,741 12/1969 Yoshida et a1 r 96/100 3,583,971 6/1971 Yoshida et a1 96/100 3,642,485 2/1972 Oishi et a1 96/9 Jan. 8, 1974 3,667,956 6/1972 lwama et al. 96/100 Primary Examiner.1. Travis Brown Attorney-Eric 1-1. Waters et al.

[ 5 7 ABSTRACT A compound of the formula:

corrmcnmo-Q-wam III N COOH 8 Claims, No Drawings l 2 LIGHT SENSITIVE SILVER HALIDE COLOR This coupler when dispersed in an organic solvent dis- PIIOTOGRAPHIC MATERIAL plays quite excellent efficiencies as a protected coupler CROSS REFERENCE To RELATED for light-sensitive silver halide color photographic material. However, the ar lazo com onent of said cou ler APPLICATIONS 5 has to be prepared thiough ver complex steps, and

This application is a continuation-in-part application therefore the coupler cannot but become relatively exof Ser. No. 28,083, filed Apr. 13, 1970 now abanpe siv doned. In addition, Japanese Patent Publication No. This invention relates to a light-sensitive silver halide p g to 3,459,552

color photographic material containing a cyan coupler discloses couplers of the formula usable in the form of a solution in an organic solvent, Y

said cyan coupler providing auto-masking mechanism for the light-sensitive color photographic material so as OH to compensate for the deficient color reproductivity of A I said material. CONHR' Almost all of the cyan couplers used as color formers in light-sensitive color photographic materials are compounds of the l-naphthol-Z-carboxylic acid or orthoaminophenol type. Particularly, cyan colored couplers having an arylazo group at their 4-position have been utilized as colored couplers provided with autornasking mechanism so as to compensate for deficiencies in color reproductivityofcolor photographic materials concerned.

CODE

For example, US. Pat. No. 3,034,892 disclosesauto- ""f" masking cyan couplers represented by the formula wherein R is a lower alkyl g py and is a y clic aryl group having nine or morecarbon atoms and containing at least one alkoxycarbonyl group; Japanese Patent Publication No. 11,304, 1967 corresponding v WQ ONHwHDXOYRZ :loullJS. Pat. No. 3,481,7l1discloses couplers of the for- I OH N I I CONHR CORa p 40 N g h m W g H I wherein X is an integer of 0 to 4, Y is 0 to 1, R is one 000R member selected from the group consisting of phenyl 5 groups, alkyl groups having 6 to 15 carbon atoms, al-

kyl-substituted phenyl groups and alkyl-substituted Rx phenoxyphenyl groups, and R is a straight chain or branched-chain alkyl group having one to four carbon atoms. The said United States patent describes as an example of said couplers a compound of the formula 5 wherein R is a branched alkyl group having six or more carbon atoms, and R is a lower alkyl group; US. Pat. No. 2,521,908 discloses couplers of the formula OH, 0H /X CON OONHwHDFa sCM, f

I tCsHu N N V H l r R1 0 OCH:

(I) 5 wherein X is a hydrogen atom or an alkyl group, Y is a monocyclic aryl group or an aralkyl group, and R, is

a monocyclic aryl group, e.g.,

c o 02m;

US. Pat. No. 2,706,684 discloses couplers of the formula CON/ wherein R and R are individually a hydrogen atom or an alkyl or aryl group, R is an alkyl, alkylene, aryl, amino, alkoxy or aryloxy group, R is a carboxy, aryloxy, carbonyl, acyl, sulfo or nitro group, and n is l to These couplers, however, when used in light-sensitive color photographic materials have considerably more drawbacks as compared with the aforesaid coupler (I). For example, these couplers have the absorption maximum at a suitable spectral region but the resulting cyan dye images have no desirable color phase as a negative image. Further, it is difficult to find a color sensitizing dye suitable for positive color sensitive material which is to be adapted to said negative image. Still further, the above-mentioned couplers have less of a disadvantage with respect to spectral absorption but are extremely low (about one-half) in emulsion speed as compared with the coupler (I) and inferior in graininess of the resulting color images. Because of their properties, the protected type colored cyan couplers of Japanese Pat. Publication No. l 1,304/1967 are used for negative sensitive materials. It is therefore desirable that couplers have such properties that they are excellent in solubility in organic solvents, favorable in auto-masking effects (broad in the range of isospecific points of blue and green portions), high in speed and prominent in graininess of the resulting images.

Couplers having all such properties have, of course, not been provided hitherto, but the coupler (I) has many desirable properties. However, when the coupler (I) is actually dissolved in an organic solvent such as tricresyl phosphate or the like and is finely dispersed in an aqueous gelatin solution, the resulting dispersion is somewhat low in stability and the dispersed particles frequently unite with each other when the dispersion is allowed to stand for a long time. Further, even if the COCH of the arylazo group is varied to --COC H -COC H-, or the like, no substantial change is seen in solubility. Moreover, there is a new disadvantage that if said --COCH is varied to COC H the coupler (1) brings about a marked color variation when subjected to ordinary color development and becomes unusable in practice.

The present invention provides couplers which are free from the above-mentioned disadvantages.

That is, the present invention is concerned with lightsensitive silver halide color photographic materials characterized by containing a coupler having the formula (\OCONH(CHz) 0tC H N II N I COOR wherein n is an integer of l to 4, and R is a lower alkyl group.

Concrete examples of the couplers employed in the present invention are as shown below.

1 l-Hydroxy-4-( 2-carboethoxyphenylazo)-N-[8- (2 ,4-di-t-amylphenoxy )-butyl 1 -2-naphtham ide to sHu l N II N COOC;H

m.p. 169170C.

2. l-Hydroxy-4-(Z-carbomethoxyphenylazo )-N-[ 8- (2,4-di-t-amylphenoxy)-butyl]-2-naphthamide.

3. l -Hydroxy-4-( 2-carbo-n-propyloxyphenylazo)-N- [8-( 2 ,4-di-t-amylphenoxy )-butyl ]-2-naphtharnide.

(Im AOcortmcmmQ-emm 1 tCsHu 111 II N I m.p. HES-128C.

4. l-Hydroxy-4-( 2-carbomethoxyphenylazo)-N-[ 6- (2,4-di-t-amylph enoxy )-propyl]-2-naphthamide.

on f o omucmno-Q-mm l V tCrHn I N H N I -C 0 OCH:

m.p. 188-189G.

0 oNHwHmOQwEI-Jm COOCz t m.p. 187-188O.

on A c 0NH cH3 .0-i0n1n k t' sfiu V I N II N -7. 1-Hydroxy-4-(2-carboethoxyphenylazo)-N-(2,4- di-t-amylphenoxy )-methyl-2-naphtl1amide.

m.p. 195-19sc.

Synthesis examples of the couplers used in the present invention are set forth below.

Synthesis Example 1 Synthesis of l-hydroxy-4-(2-carboethoxyphenylazo)- N-['6-(2,4-di-t-arnylphenoxy)-butyl]-2-naphthamide (coupler (1)):

Into a mixture comprising 220 g. of ethyl oaminobenzoate, 400 cc. of concentrated hydrochloric acid and 800 cc. of water was dropped with stirring at 0 i 5C. over a period of about 15 minutes a mixture comprising 92 g. of NaNO and 300 cc. of water, and the resulting mixture was stirred at 0 i 5C. for 30 minutes to prepare a diazo solution. The thus prepared diazo solution was dropped with stirring at 5 i 5C. over a period of 30 minutes into a solution of 600 g. of l -hydroxy-N-[8-(2,4-di-t'amylphenoxy)-butyl1-2- naphthamide in 18 liters of pyridine, and the resulting mixture was stirred at below 10C. for 1 hour.

The reaction mixture was charged into 25 liters of water, and the deposited red crystals were recovered by filtration. After washing with water, the crystals were dried and then recrystallized from 55 liters of npropanol to form a red powder. This red powder was washed with 300 ml. of methanol and then dried to obtain 750 g. of l-hydroxy-4-(2-carboethoxyphenylazo- N-[ 8-(2,4-di-t-amylphenoxy)-butyl]-2-naphthamide, coupler (l), as a red powder. m.p. 169 170C., yield 92 percent.

Elementary analysis:

C H N (M Calculated 73.70 7.58 6.45 Found 73.90 7.66 638 Synthesis Example 2 Synthesis of l-hydroxy-4-( 2-carbo-npropyloxyphenylazo)-N-[8-(2,4-di-t-amylphenoxy)- butyl]-2-naphthamide (coupler (3)):

The same procedures as in Synthesis Example 1 were effected, except that 239 g. of n-propyl oaminobenzoate was used in place of the ethyl oaminobenzoate. The resulting red powder was recrystallized from 75 liters of alcohol to obtain 700 g. of lhyd rox y-4-( 2-carbo-n-propyloxyphenylazo )-N-[ 6-( 2,4- di-t-amylphenoxy)-butyl]-2-naphthamide, coupler (3), as a red powder. m.p. 126- 128C., yield 83.3 percent.

Elementary analysis:

c ll'(%) N(%) Calculated 73.95 7.72 6.21 Found 74.06 7.59 6.15

Synthesis Example 3 Synthesis of 1-hydroxy-4-(2- carbomethoxyphenylazo)-N-[y-(2,4-di-tamylphenoxy)-propyll-2-naphthamide (coupler (4)):

The same procedures as in Synthesis Example 1 were effected, except that 201 g. of methyl o-aminobenzoate was used in place of the ethyl o-aminobenzoate and 582 g. of 1-hydroxy-N-['y-(2,4-di-t-amylphenoxy)- propy1]-2-naphthamide was used in place of the 1- hydroxy-N-[8-(2,4-di-t-amylphenoxy)-butyl]-2- naphthamide. The resulting red powder was recrystallized from 170 liters of n-propanol to obtain 740 g. of l-hydroxy-4-( 2-carbomethoxyph'enylazo)-N-['y-( 2,4- di-t-amylphenoxy)-propyl]-2-naphthamide, coupler (4), as a red powder. m.p. 188 189C., yiled 94.3 percent.

Elementary analysis:

C H N (M Calculated 73.17 7.27 6.74 Found 73.12 7.35 6.65

Synthesis Example 4 Synthesis of 1-hydroxy-4-(2-carboethoxyphenylazo)- N-[B-(2,4-di-t-amylphenoxy)-ethyl]-2-naphthamide (coupler (5)):

The same procedures as in Synthesis Example 1 were effected, except that 563 g. of l-hydroxy-N[B-(2,4-dit-amylphenoxy)-ethyl]-2-naphthamide was used in place of the 1-hydroxy-N-[8-(2,4-di-t-amylphenoxy)- butyl]-2-naphthamide. The resulting red powder was recrystallized from liters of n-propanol to obtain 750 g. of l-hydroxy-4-(2-carboethoxyphenylazo)-N-.

8 [B-(2,4-di-t-amylphenoxy)-ethyl]-2-naphthamide as a red powder. m.p. 187 188C, yield 95.5 percent.

Elementary analysis:

C H (96) N (76) Calculated 73.17 7.27 6.74 Found 73.05 7.30 6.70

Excellent properties of the couplers used in the present invention are shown below with reference to test examples.

Test Example 1 The couplers used in the present invention and other couplers were compared to each other in solubility for tricresyl phosphate in such a manner that 1 g. of each coupler was dissolved at 80C. in tricresyl phosphate and then allowed to stand at 20C., and the time required for initiation of the crystallization of said coupler was measured to obtain the results as shown below.

Test Example 2 Couplers of the present invention which were of the formula shown below and the known coupler of the same formula, except that R' was different, were tested for solubility in a high boiling solvent to obtain the re- 1 sults set forth in the table below. (One gram of each coupler was thoroughly dissolved in tricresyl phosphate and the solubility thereof was represented by the minimum amount (cc.) of the tricresyl phosphate in which .the coupler did not deposit at room temperature for more than 24 hours.)

Red prussiate 100 g. A CONHwHmOTQTwBH Potassium bromide 20 g. [1511 Water to make 1,000 ml.

(pH 6.9 i 0.3) q Fixing solution: H, Hypo 200 g.

1 Sodium sulfite 20 g.

COR Acetic acid (28 percent) 45 ml.

Boric acid 7.5 g.

Potash alum g. Water to make 1,000 ml. (pH 4.5 t 0.2)

Known Present coupler coupler R -cu -ocH, oc,n, -o(n)c,u, -o n)c.u,

Amount of IO 15 30 10 12 tricresyl phosphate The couplers e mployed in the present invention may be optionally varied in solubility. Moreover, all these 2 couplers are excellent in emulsion property and masking property, and they always give light-sensitive color photographic materials having uniform photographic properties.

The present invention is illustrated in detail below with reference to examples.

Example 1 minute to prepare a coupler dispersion. 13.5 Parts of this dispersion were added with stirring at 35C. to 100 parts of a light-sensitive silver iodobromide emulsion containing a red light-sensitive sensitizing dye, and the resulting mixture was coated on a film support and then dried to obtain a red light-sensitive color photographic material.

The thus obtained photographic material was exposed to red light through an optical wedge and was subjected to ordinary color development using a color developer of the following composition:

Color developer:

N,N-Diethyl-p-aminoaniline sulfate 2.0 g.

Sodium sulfite 2.0 g.

Sodium carbonate (monohydrate) 500 g.

Hydroxylamine hydrochloride 1.5 g.

Potassium bromide 1.0 g.

Water to make 1,000 ml.

(pH 10.8 i 0.1)

Thereafter, the photographic material was bleached and fixed by use of a bleaching solution and a fixingsolution of the compositions shown below to remove undeveloped silver halide and by-produced reduced silver.

In the above manner, a cyan colored negative image and a red positive image comprising unreacted residual coupler were obtained. This red positive image showed a sufficient red color and had isospecific points of 405 mu and 540 mu.

Example 2 A mixture comprising 1 part of the coupler (3) and 3 parts of l-hydroxy-N-[6-(2.,4-di-t-amylphen0xy)- butyl]-2-naphthamide was dissolved with stirring at C. in 10 parts ofT.C.P., and was added to parts of a 10 percent aqueous gelatin solution kept at 60C., and the mixed solution was charged with 2 parts of a 10 percent aqueous sodium alkylbenzene-sulfonate solution. Subsequently, the liquid was. stirred at about 65C. for 5 minutes by use of a high speed rotary mixer. This procedure was repeated 5 times at intervals of 1 minute to prepare a coupler dispersion. 10 Parts of this coupler dispersion was added to 100 parts of a high speed lightsensitive silver iodobromide emulsion containing a rod light-sensitive sensitizing dye, and the resulting mixture was treated in the same manner as in Example 1 to obtain a red light-sensitive color photographic material.

This photographic material was exposed to red light through an optical wedge and was color-developed, bleached and fixed in the same manner as in Example 1, whereby a cyan colored negative image and an excellent red positiveimage were obtained simultaneously. Transparency also was quite excellent.

Example 3 Example 4 A mixture comprising 0.3 part of the coupler (1), 0.7 part of the coupler (6) and 3 parts of 1-hydroxy-N-[8- (2,4-di-t-amylphenoxy )-butyl ]-2-naphthamide was treated in the same manner as in Example 2 to obtain a red light-sensitive color photographic material. This photographic material was exposed to red light and then treated in the same manner as in Example 2, whereby a cyan colored negative image and an excellent red positive image were obtained simultaneously.

Example 5 This experiment was conducted to compare the photographic properties of a cyan coupler according to the present invention with three cyan couplers of the prior art having a closely related structure.

The couplers tested were as follows: Present coupler (1) Control coupler B (Coupler 1V, U.S. Pat. No.-

3,481,741) See Test Example 1 Control coupler C (Compound 11, U.S. Pat. No.

Control coupler D (Coupler lll, U.S. Pat. No.

C O (CHz)11CHa l G O O C2H Bleaching solution:

to C. Two parts of a 10 percent aqueous solution of sodium alkylbenzene sulfonate were added and dispersed with mixing by means of a high speed mixer for 5 minutes at C. followed by stopping the stirring for 1 minute. This was repeated 5 times to give a dispersion of the coupler.

Color developer: 6.

N,N-diethyl-para-aminoaniline sulfate 2.0

Sodium sulfite 2.0

Sodium carbonate (mono-hydrate) 50.0

Hydroxylamine hydrochloride 1.5

Potassium bromide 1.0

Water to make 1,000 ml. (pH 1080.1).

Thus developed photographic films were bleached and fixed using the bleaching solution and the fixing sslution having the following formulas, respectively, to remove the undeveloped silver halide and thus reduced silver.

Potassium ferricyanide 100 Potassium bromide 20 Water to make 1,000 ml (pH 6.9 0.3). Fixing solution:

Sodium thiosulfate g. 200 Sodium Sulfite g. 20 Acetic acid (28%) ml. 45 Boric acid g. 7.5 Potassium alum g. 20

Water to make 1,000 ml. (pH 4.5 0.2). The photographic properties were as follows:

Colored cyan Relative speed Fog Gamma Light fastness of Maximum absorption Maximum absorption of coupler masking dye of masking dye developed color image (1) 320 0.04 0.46 83% SOOmp. 690m B 200 0.05 0.33 72" 440-500" 690" C 100 0.04 0.23 60" 506" 690" D 230 0.04 0.30 78" 518" 720" *This value is a percentage of the residual density of the masking dye as compa ed with the origir aldegsity gfstfle when an image was subject to a Fado-O-Meter for 50 hours.

into 10 parts of tricresyl phosphate was dissolved 1.25 parts of coupler (1) with stirring at 80C., and the solution was added to parts of an aqueous 10 percent gelatin solution that had been preliminarily heated As can be seen, coupler (l) and coupler C both are equally excellent in spectral characteristics including spectral and maximum absorptions of masking dye and colored dye images. However, the coupler (1) is much v at 440 my and 500 mu, as shown below:

more excellent in speed and light fastness of masking @5551; an integer of l to 4 and R is a lower alkyl dye than coupler C. Particularly with respect to the group. speed, coupler ('l) is three times faster than coupler C. 2. A light-sensitive silver halide color photographic This means that the coupler (1) is very preferred for material as claimed in claim 1, wherein said coupler is auto-masking mechanism when it is jointly used with a a compound of the following structure colorless coupler. Such an unexpected technical advantage of coupler (1) over coupler C results from the on structural difference between the two, in that the azo portion of coupler (I) is of the ester (COOC H5) A comucnmo uwum type whereas that of coupler C is of the ketone @5 -cocn type.

In both coupler (l) and the coupler B; the azo portions are of the ester (-COOR) type, which show good 'l spectral characteristics. However, coupler B disadvanl tageously has undesired spectral absorption of masking -COOC2H5 dye, which is due to the inclusion of a branched alkyl group. The emulsion test indicates that coupler B has a broad absorption comprising two absorption maxima silver halide col or photographic material as claimed in claim 1, wherein said coupler is a compound of the following structure COOCHa wavel engtb. (m u) This means that coupler B is not appropriate as colored cyan coupler because its maskingaction is too excessive in the short wavelength region.

Both coupler (l) and coupler D which have the azo portion of the ester type are equally competent in pho- 0 tographic properties. However, coupler D is detrimentally undesirable because of its having a maximum absorption at a verylong wavelength site, i.e., 720 mp. K/

4, light-sensitive silver halide color photographic material as claimed in claim 1, wherein said coupler is a compound of the following structure This is considered to be due to the existence of an ani- K551i lide moiety at the 2-position of the naphthol nucleus. Ill n Thus it can be seen that the particular structure of I I the couplers of the present invention provide an unexpected combination of desirable solubility and photo Coooafiflm graphic properties not exhibited by prior art couplers.

What we claim is: 1. A light-sensitive silver halide color photographic material incorporated with a couple! having the material as claimed in claim 1, wherein said coupler is mula a compound of the following structure II II i 5 COOR -COOCH:

53; light sensitive silver halide color photographic 15 16 6. A light-sensitive silver halide color photographic 8. A light-sensitive silver halide color photographic material as claimed in claim 1, wherein said coupler is material as claimed in claim 1, wherein said coupler is a compound of the following structure a compound of the following structure OH v ooNmcHnmQtcmu K/ a n OH N l c 0NH-cH,-o tcmn COOC:H5

7. A light-sensitive silver halide color photographic a compound of the following structure material as claimed in claim 1 wherein said cou ler is p COOC5H5 conmcmpo-Qwun V tsHu ll N COOC4H0(I1) l 

2. A light-sensitive silver halide color photographic material as claimed in claim 1, wherein said coupler is a compound of the following structure
 3. A light-sensitive silver halide color photographic material as claimed in claim 1, wherein said coupler is a compound of the following structure
 4. A light-sensitive silver halide color photographic material as claimed in claim 1, wherein said coupler is a compound of the following structure
 5. A light-sensitive silver halide color photographic material as claimed in claim 1, wherein said coupler is a compound of the following structure
 6. A light-sensitive silver halide color photographic material as claimed in claim 1, wherein said coupler is a compound of the following structure
 7. A light-sensitive silver halide color photographic material as claimed in claim 1, wherein said coupler is a compound of the following structure
 8. A light-sensitive silver halide color photographic material as claimed in claim 1, wherein said coupler is a compound of the following structure 